WO2022172603A1 - Matériau actif, son procédé de production, électrode et batterie secondaire - Google Patents

Matériau actif, son procédé de production, électrode et batterie secondaire Download PDF

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WO2022172603A1
WO2022172603A1 PCT/JP2021/047210 JP2021047210W WO2022172603A1 WO 2022172603 A1 WO2022172603 A1 WO 2022172603A1 JP 2021047210 W JP2021047210 W JP 2021047210W WO 2022172603 A1 WO2022172603 A1 WO 2022172603A1
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active material
peak
atomic
silicate glass
negative electrode
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PCT/JP2021/047210
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English (en)
Japanese (ja)
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大輔 伊藤
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株式会社村田製作所
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Priority to CN202180093540.7A priority Critical patent/CN116830313A/zh
Priority to JP2022581220A priority patent/JPWO2022172603A1/ja
Publication of WO2022172603A1 publication Critical patent/WO2022172603A1/fr
Priority to US18/227,118 priority patent/US20230387409A1/en

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C11/00—Multi-cellular glass ; Porous or hollow glass or glass particles
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/06—Glass compositions containing silica with more than 90% silica by weight, e.g. quartz
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/097—Glass compositions containing silica with 40% to 90% silica, by weight containing phosphorus, niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/11—Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C4/00—Compositions for glass with special properties
    • C03C4/14—Compositions for glass with special properties for electro-conductive glass
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2204/00—Glasses, glazes or enamels with special properties
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • This technology relates to an active material and its manufacturing method, as well as an electrode and a secondary battery.
  • the secondary battery comprises electrodes (a positive electrode and a negative electrode) as well as an electrolyte, and the electrodes contain active materials that participate in electrode reactions. Since the configuration of a secondary battery affects battery characteristics, various studies have been made on the configuration of the secondary battery.
  • silicon oxide (SiO x ) powder is obtained by heating silicon dioxide to generate silicon oxide gas and condensing the silicon oxide gas (for example, Patent Documents 1 and 2). reference.).
  • silicon oxide gas for example, Patent Documents 1 and 2.
  • a different element is added to the silicon oxide (see Patent Documents 3 and 4, for example).
  • a pyroxene silicate compound is used, and a heat reduction product of tin oxide (SnO x ) using a reducing gas is used (for example, Patent Document 5 , 6).
  • an active material a method for producing the same, an electrode, and a secondary battery that are capable of obtaining excellent charge-discharge characteristics and excellent swelling characteristics are desired.
  • the active material of one embodiment of the present technology includes silicon, oxygen, a first element containing at least one of boron and phosphorus, an alkali metal element, a transition element and a typical element (silicon, oxygen, boron, phosphorus, excluding alkali metal elements and alkaline earth metal elements), and a third element containing an alkaline earth metal element as constituent elements.
  • the content of silicon in all the constituent elements excluding oxygen and carbon is 60 atomic % or more and 98 atomic % or less, and the content of the first element in all the constituent elements is 1 atomic % or more and 25 atomic % or less.
  • the content of the second element in all the constituent elements is 1 atomic % or more and 34 atomic % or less
  • the content of the third element in all the constituent elements is 0 atomic % or more and 6 atomic % or less.
  • the binding energy is 102 eV or more and 105 eV or less.
  • a first peak is detected that has an apex within a certain range and a shoulder on the side of the lower binding energy than the apex.
  • the Raman shift has a peak within a range of 435 cm -1 or more and 465 cm -1 or less.
  • a second peak is detected.
  • Pore size distribution measured using a mercury intrusion method horizontal axis is pore size ( ⁇ m) and vertical axis is rate of change in amount of mercury infiltration, pore size is 0.01 ⁇ m
  • a third peak is detected that has an apex within a range that is greater than or equal to 10 ⁇ m and less than or equal to 10 ⁇ m.
  • a method for producing an active material according to an embodiment of the present technology comprises silicon, oxygen, a first element containing at least one of boron and phosphorus, an alkali metal element, a transition element and a typical element (silicon, oxygen, boron , phosphorus, alkali metal elements and alkaline earth metal elements), and a third element containing an alkaline earth metal element as constituent elements, and a plurality of fine elements
  • a silicate glass having pores is prepared, the silicate glass is mixed with a carbon source to obtain a mixture of the silicate glass and the carbon source, and the mixture is heated to obtain silicon, oxygen, the first element, An active material containing the second element and the third element as constituent elements is manufactured.
  • the content of silicon in the active material (all constituent elements excluding oxygen and carbon) is 60 atomic % or more and 98 atomic % or less, and the content of the first element in the active material is 1 atomic % or more and 25 atomic %.
  • the content of the second element in the active material is 1 atomic % or more and 34 atomic % or less, and the content of the third element in the active material is 0 atomic % or more and 6 atomic % or less.
  • An electrode of an embodiment of the present technology includes an active material, and the active material has a configuration similar to that of the active material of the embodiment of the present technology described above.
  • a secondary battery of an embodiment of the present technology includes a positive electrode, a negative electrode containing an active material, and an electrolytic solution, and the active material has the same configuration as the active material of the embodiment of the present technology. have.
  • the active material contains silicon, oxygen, the first element, the second element and the third element as constituent elements and has a plurality of pores and the content of each constituent element satisfies the above conditions.
  • a first peak was detected in the XPS spectrum of Si2p measured using X-ray photoelectron spectroscopy
  • a second peak was detected in the Raman spectrum measured using Raman spectroscopy
  • mercury intrusion A third peak is detected in the pore size distribution measured using the method. Therefore, excellent charge/discharge characteristics and excellent swelling characteristics can be obtained.
  • a silicate glass containing silicon, oxygen, a first element, a second element, and a third element as constituent elements and having a plurality of pores is used as a carbon source. After mixing, the mixture of the silicate glass and the carbon source is heated to produce an active material, and the content of each constituent element in the active material satisfies the above conditions. Therefore, an active material having excellent charge/discharge characteristics and excellent swelling characteristics can be obtained.
  • FIG. 4 is a cross-sectional view showing another configuration of the active material of one embodiment of the present technology; It is an example of the analysis result (XPS spectrum of Si2p) of the active material using XPS. It is an example of the analysis result (Raman spectrum) of the active material using Raman spectroscopy. It is an example of the analysis result (pore distribution) of the active material using the mercury intrusion method. It is a flow chart for explaining a manufacturing method of an active material of one embodiment of this art.
  • 1 is a perspective view showing a configuration of an electrode and a secondary battery (laminate film type) according to an embodiment of the present technology; FIG. FIG.
  • FIG. 8 is a cross-sectional view showing the configuration of the battery element shown in FIG. 7; 9 is a plan view showing the configuration of each of the positive electrode and the negative electrode shown in FIG. 8.
  • FIG. FIG. 3 is a block diagram showing the configuration of an application example of a secondary battery;
  • FIG. 2 is a cross-sectional view showing the configuration of a test secondary battery (coin type);
  • Active Material Metal for Producing Active Material
  • an active material according to an embodiment of the present technology will be described.
  • the manufacturing method of the active material of one embodiment of this technique is a method of manufacturing the active material described here, the manufacturing method of the active material will also be described below.
  • This active material is a substance involved in the electrode reaction. More specifically, the active material is a material that can store and release an electrode reactant, and is used as an electrode material in an electrochemical device that operates using an electrode reaction. In this case, the active material absorbs and releases the electrode reactant in an ionic state.
  • the active material may be used as an electrode material for a positive electrode (positive electrode active material), or may be used as an electrode material for a negative electrode (negative electrode active material).
  • the application of the active material is not particularly limited as long as it is an electrochemical device that operates using an electrode reaction, but specific examples include secondary batteries and capacitors.
  • the type of electrode reactant is not particularly limited, but specifically light metals such as alkali metals, alkaline earth metals, and aluminum.
  • Alkali metals include lithium, sodium and potassium
  • alkaline earth metals include beryllium, magnesium and calcium.
  • FIGS. 1 and 2 represents a cross-sectional configuration of an active material 100, which is an example of an active material.
  • This active material 100 has a plurality of pores 103 as shown in FIGS. 1 and 2, respectively.
  • the active material 100 comprises a central portion 101 and a covering portion 102 as shown in FIG. 1, and the central portion 101 may have a plurality of pores 103 as described above.
  • the active material 100 has a central portion 101 and a covering portion 102, as shown in FIG. may 1 and 2 show the case where the three-dimensional shape of the central portion 101 is spherical for the sake of simplification of the illustration, but the three-dimensional shape of the central portion 101 is limited not.
  • the central portion 101 is the main portion of the active material 100 that stores and releases the electrode reactant.
  • This central portion 101 has a plurality of pores 103 as described above, and more specifically, a carbon-reduced silicate glass having a plurality of pores 103 (hereinafter referred to as “porous carbon-reduced silicic acid (referred to as “glass”).
  • This porous carbon-reduced silicate glass is different from ordinary silicate glass (hereinafter simply referred to as “silicate glass”).
  • silicate glass having pores 103 hereinafter referred to as “porous silicate glass” is a carbon-reduction-treated material.
  • the number of types of porous carbon-reduced silicate glass may be one, or two or more.
  • the use of the carbon source as a reducing agent accelerates the reduction reaction of the raw material porous silicate glass.
  • the porous silicate glass is reduced (activated) so that it can absorb and release the electrode reactant sufficiently. That is, in a normal reduction treatment using a reducing gas as a reducing agent, porous silicate glass is hardly reduced, whereas in a special reduction treatment (carbon reduction treatment) using a carbon source as a reducing agent, Porous silicate glass is fully reduced. Accordingly, the porous carbon-reduced silicate glass has physical properties different from those of silicate glass. Details of physical properties of the porous carbon-reduced silicate glass will be described later.
  • the porous carbon-reduced silicate glass contains silicon, oxygen, a first element, a second element, and a third element as constituent elements.
  • the content of each constituent element in all constituent elements excluding oxygen and carbon is set to be within a predetermined range.
  • the content of each constituent element indicates what atomic percent the content of each constituent element corresponds to when the content of all constituent elements excluding oxygen and carbon is 100 atomic percent.
  • the content (atomic %) of each constituent element was measured by scanning electron microscope/energy dispersive X-ray spectrometry (SEM: Scanning Electron Microscope/EDX: Energy dispersive X-ray spectrometry). Calculated based on acid glass analysis results.
  • Silicon is the main constituent element in porous carbon-reduced silicate glasses.
  • the content of silicon in all constituent elements excluding oxygen and carbon is 60 atomic % to 98 atomic %.
  • the porous carbon-reduced silicate glass contains SiO x (x satisfies 0 ⁇ x ⁇ 2) as a main component.
  • SiO x nano-silicon is considered to be dispersed in amorphous silicon dioxide (SiO 2 ).
  • SiO x it is considered that silicon, which can sufficiently absorb and release the electrode reactant, is present in the glass component.
  • the first element contains one or more of network forming elements, and more specifically contains one or both of boron and phosphorus. This is because, when the porous silicate glass contains the first element as a constituent element together with silicon and oxygen, the porous silicate glass is easily reduced sufficiently in the carbon reduction treatment. This facilitates the easy and stable formation of porous carbon-reduced silicate glass using carbon reduction treatment.
  • a network-forming element is a general term for a series of elements capable of forming a network-forming body (network-forming oxide). Therefore, the first element may contain germanium and the like in addition to boron and phosphorus described above.
  • the content of the first element in all constituent elements excluding oxygen and carbon is 1 atomic % to 25 atomic %. This is because the porous silicate glass is easily reduced sufficiently in the carbon reduction treatment.
  • the content of the first element is the sum of the contents of each element.
  • the fact that the content is the sum of the contents of the respective constituent elements when the number of types of elements is two or more as described above also applies to the content of the second element and the content of the third element, which will be described later. .
  • the second element contains one or more of alkali metal elements, transition elements and typical elements. This second element, unlike the third element described later, has little effect on the reducibility of the porous silicate glass in the carbon reduction treatment even if it is contained as a constituent element in the porous silicate glass. is. Therefore, even if the porous silicate glass contains the second element as a constituent element, the porous silicate glass is sufficiently reduced in the carbon reduction treatment.
  • the alkali metal element is a general term for a series of elements belonging to Group 1 of the long period periodic table, specifically lithium, sodium and potassium.
  • the transition element is a general term for a series of elements belonging to Groups 3 to 11 of the long period periodic table, specifically scandium, titanium, iron, zirconium and cerium.
  • the type of transition element is not particularly limited as long as it is an element belonging to Groups 3 to 11 of the long period periodic table. may be other elements.
  • Typical elements are a general term for a series of elements belonging to Groups 1, 2 and 12-18 of the long period periodic table.
  • silicon, oxygen, boron, phosphorus, alkali metal elements and alkaline earth metal elements are excluded from the typical elements explained here. Therefore, typical elements described here are specifically aluminum, sulfur, chlorine, zinc, bismuth, and the like.
  • the type of typical element is not particularly limited as long as it is an element belonging to Groups 1, 2 and 12 to 18 of the long period periodic table. may be an element of
  • the content of the second element in all constituent elements excluding oxygen and carbon is 1 atomic % to 34 atomic %. This is because even if the porous silicate glass contains the second element as a constituent element, the porous silicate glass can be sufficiently reduced in the carbon reduction treatment.
  • the third element is any constituent element of the porous carbon-reduced silicate glass. Therefore, the porous carbon-reduced silicate glass may or may not contain the third element as a constituent element.
  • the third element contains one or more of alkaline earth metal elements.
  • This alkaline earth metal element is a general term for a series of elements belonging to group 2 of the long period periodic table, and specifically includes magnesium, calcium, strontium, barium, and the like.
  • the content of the third element in all constituent elements excluding oxygen and carbon is 0 atomic % to 6 atomic %.
  • the reason why the lower limit of the content of the third element is 0 atomic % is that the third element is an arbitrary constituent element of the porous carbon-reduced silicate glass, as described above. This is because the silicate glass may not contain the third element as a constituent element.
  • the upper limit of the content of the third element is 6 atomic % because, as described above, the third element affects the reducibility of the porous silicate glass in the carbon reduction treatment. This is because the contents of the three elements must be within a range that does not affect the reducibility of the porous silicate glass in the carbon reduction treatment.
  • the content of the tertiary element is greater than 6 atomic %, the amount of the tertiary element present in the porous silicate glass is too large, resulting in the formation of porous silica in the carbon reduction treatment. Substantially no porous carbon-reduced silicate glass is formed because the acid glass is hardly reduced.
  • the content of the third element is 6 atomic % or less, the carbon reduction Porous carbon-reduced silicate glass is substantially formed because the porous silicate glass is susceptible to reduction in the process.
  • the covering portion 102 covers part or all of the surface of the central portion 101 . However, when the covering portion 102 partially covers the surface of the central portion 101, even if the surface of the central portion 101 is covered with a plurality of covering portions 102 at a plurality of locations separated from each other. good.
  • the covering portion 102 contains carbon as a constituent element, so it has conductivity. Since the coating portion 102 having conductivity covers the surface of the central portion 101, the electron conductivity of the active material 100 is improved as compared with the case where the coating portion 102 does not cover the surface of the central portion 101. because it improves.
  • the material for forming the covering portion 102 is not particularly limited as long as it contains carbon as a constituent element.
  • the coating portion 102 when a mixture of porous silicate glass and a reducing agent (carbon source) is heated in an active material manufacturing process (carbon reduction treatment), the coating portion 102 is formed so that the carbon It is a coating formed on the surface of the central portion 101 using thermal decomposition of the source.
  • the covering portion 102 may contain the carbon source as it is, may contain the decomposition products of the carbon source (organic decomposition carbon), or may contain both.
  • the covering portion 102 may have a plurality of pores 103 as described above, or may not have a plurality of pores 103. That is, the pores 103 are provided only in the central portion 101 and may not be provided in the covering portion 102, or are provided not only in the central portion 101 but also in the covering portion 102. may be Whether or not the covering portion 102 has a plurality of pores 103 is determined according to the type of the carbon source described above. The details of the relationship between the type of carbon source and the presence or absence of the plurality of pores 103 will be described later.
  • the average pore size of the plurality of pores 103 provided in the central portion 101 and the average pore size of the plurality of pores 103 provided in the covering portion 102 may be the same or different. good.
  • the average diameter of the plurality of pores 103 provided in the covering portion 102 is set in the central portion 101. It tends to be smaller than the average pore size of the plurality of pores 103 provided.
  • the thickness of the covering portion 102 is not particularly limited. If the covering portion 102 exists even slightly on the surface of the central portion 101, the electronic conductivity of the active material 100 is improved compared to the case where the covering portion 102 does not exist on the surface of the central portion 101 at all. is.
  • FIG. 3 shows an example of an analysis result (XPS spectrum of Si2p) of the active material 100 using XPS to explain the first physical property.
  • the horizontal axis indicates binding energy (eV) and the vertical axis indicates spectral intensity.
  • the XPS spectrum (broken line) of the porous silicate glass is also shown together with the XPS spectrum (solid line) of the porous carbon-reduced silicate glass. That is, a porous carbon-reduced silicate glass from which the XPS spectrum (solid line) is detected can be obtained by subjecting the porous silicate glass from which the XPS spectrum (broken line) is detected to carbon reduction treatment. Note that in FIG. 3, the range in which the binding energy is 102 eV to 105 eV is shaded.
  • porous carbon-reduced silicate glass has physical properties different from those of porous silicate glass in the analysis results using XPS (shape of XPS spectrum).
  • the peak XA (first peak) is detected in the XPS spectrum (solid line) of the porous carbon-reduced silicate glass.
  • This peak XA has an apex XAT within a range where the binding energy is 102 eV to 105 eV, and has a shoulder XAS on the side where the binding energy is smaller than the apex XAT (right side in FIG. 3).
  • This shoulder portion XAS is a shoulder-like portion in which a part of the peak XA having the apex XAT protrudes toward the low binding energy side, that is, a step-like portion.
  • peak XB is detected in the XPS spectrum (dashed line) for silicate glass.
  • This peak XB has a vertex XBT within a range where the binding energy is 102 eV to 105 eV. does not have
  • the tendency described below is derived with respect to the analysis result (shape of XPS spectrum) of the active material 100 using XPS.
  • the porous carbon-reduced silicate glass since the raw material porous silicate glass is sufficiently reduced using the carbon reduction treatment, a peak XA having an apex XAT and a shoulder XAS is detected.
  • a peak XB having only the vertex XBT is detected because the carbon reduction treatment has not yet been performed. Therefore, it is possible to specify whether the analysis target is porous carbon-reduced silicate glass or porous silicate glass based on the analysis results using XPS. Therefore, the porous carbon-reduced silicate glass formed by the carbon reduction treatment has physical properties different from those of the porous silicate glass in that it has the first physical properties related to XPS described above.
  • the material of the central portion 101 of the active material 100 can be specified by the procedure described here. That is, by analyzing the central portion 101 using XPS, when peak XA is detected, the central portion 101 contains porous carbon-reduced silicate glass, whereas peak XB is detected. If so, its central portion 101 contains porous silicate glass.
  • porous silicate glass is hardly reduced by normal reduction treatment. Therefore, even if a porous silicate glass is used and subjected to a normal reduction treatment, the porous silicate glass is hardly reduced, so peak XB should be obtained instead of peak XA.
  • the peak XA related to the porous carbon-reduced silicate glass has a shoulder XAS, whereas the peak XB related to the porous silicate glass does not have a shoulder. Therefore, it is possible to identify whether the analyte is porous carbon-reduced silicate glass or porous silicate glass by the procedure described below.
  • the width in the middle of peak XA in the height direction is larger than the width in the middle of peak XB in the height direction. Therefore, the half-value width of peak XA is larger than the half-value width of peak XB, and more specifically, is 4.0 eV or more.
  • the half-value width of peak XA is 4.0 eV or more, whereas the half-value width of peak XB is not 4.0 eV or more. It is possible to specify whether the object is porous carbon-reduced silicate glass or porous silicate glass. That is, even if it is difficult to determine the presence or absence of the shoulder XAS because the shoulder XAS is small, the type of the analyte can be identified by examining the half-value width.
  • the area in the middle of peak XA is larger than the area in the middle of peak XB.
  • the area of peak XA is The ratio S2/S1 is greater than the area ratio S2/S1 of the peak XB, more specifically 0.85 or more.
  • the area S1 is the area of the Si 4+ peak
  • the area S2 is the sum of the area of the Si 0 peak, the area of the Si 1+ peak, the area of the Si 2+ peak, and the area of the Si 3+ peak. is.
  • Each of the areas S1 and S2 can be calculated using the analysis (calculation) function of the XPS device.
  • the area ratio S2/S1 of peak XA is 0.85 or more, whereas the area ratio S2/S1 of peak XB is not 0.85 or more.
  • /S1 it is also possible to identify whether the analyte is porous carbon-reduced silicate glass or porous silicate glass. That is, as described above, even if it is difficult to determine the presence or absence of the shoulder XAS because the shoulder XAS is small, the type of the analyte can be specified by examining the area ratio S2/S1.
  • FIG. 4 shows an example of analysis results (Raman spectrum) of the active material 100 using Raman spectroscopy to explain the second physical properties.
  • the horizontal axis indicates Raman shift (cm ⁇ 1 ) and the vertical axis indicates spectral intensity.
  • FIG. 4 shows the Raman spectrum (solid line) of the porous carbon-reduced silicate glass as well as the Raman spectrum (broken line) of the porous silicate glass. That is, a porous carbon-reduced silicate glass from which a Raman spectrum (solid line) is detected can be obtained by subjecting the porous silicate glass from which a Raman spectrum (broken line) is detected to carbon reduction treatment.
  • the Raman shift range of 435 cm ⁇ 1 to 465 cm ⁇ 1 is shaded.
  • the porous carbon-reduced silicate glass has different physical properties from the physical properties of the porous silicate glass in the analysis results (Raman spectrum shape) using Raman spectroscopy.
  • a peak RA (second peak) is detected in the Raman spectrum (solid line) of the porous carbon-reduced silicate glass.
  • This peak RA has an apex RAT within the Raman shift range of 435 cm ⁇ 1 to 465 cm ⁇ 1 .
  • a peak RB is detected in the Raman spectrum (broken line) for porous silicate glass.
  • This peak RB does not have an apex RBT within the range of binding energies from 435 cm ⁇ 1 to 465 cm ⁇ 1 , but has an apex RBT outside that range.
  • a peak having a binding energy within the range of 510 cm ⁇ 1 to 525 cm ⁇ 1 is detected.
  • the tendency described below is derived with respect to the analysis result (shape of Raman spectrum) of the active material 100 using Raman spectroscopy.
  • the porous carbon-reduced silicate glass since the porous silicate glass as the raw material is sufficiently reduced using the carbon reduction treatment, a peak having an apex RAT within the range of 435 cm -1 to 465 cm -1 RA is detected.
  • a peak RB having an apex RBT outside the above range is detected. Therefore, the porous carbon-reduced silicate glass formed by the carbon reduction treatment has physical properties different from those of the porous silicate glass in that it has the second physical properties related to Raman spectroscopy. is doing.
  • the material of the central portion 101 of the active material 100 can be specified by the procedure described here. That is, when peak RA is detected by analyzing central portion 101 using Raman spectroscopy, peak RB is detected, the central portion 101 contains porous silicate glass.
  • porous silicate glass is hardly reduced by normal reduction treatment. Therefore, even if the porous silicate glass is used and subjected to a normal reduction treatment, the porous silicate glass is hardly reduced, so the peak RB should be obtained without obtaining the peak RA.
  • FIG. 5 shows an example of the analysis result (pore distribution) of the active material 100 using the mercury porosimetry to explain the third physical property.
  • the horizontal axis indicates the pore size ( ⁇ m)
  • the vertical axis indicates the rate of change in the amount of mercury permeation.
  • the value of the rate of change in the amount of mercury penetration is a value normalized by setting the maximum value of the rate of change in the amount of mercury penetration in the case where the central portion 101 contains the porous carbon-reduced silicate glass to 1.
  • FIG. 5 shows the pore distribution (solid line) for an active material 100 in which the central portion 101 comprises a porous carbon-reduced silicate glass having a plurality of pores 103, and the central portion 101 does not have a plurality of pores 103. Also shown is the pore distribution (dashed line) for the active material 100, which includes carbon-reduced silicate glass (hereafter referred to as "non-porous carbon-reduced silicate glass”). This non-porous carbon-reduced silicate glass uses a carbon source as a reducing agent to obtain a silicate glass without a plurality of pores 103 (hereinafter referred to as "non-porous silicate glass") by carbon reduction. processed material.
  • FIG. 5 shows the pore distribution (solid line and broken line) when the covering portion 102 does not have the pores 103, and the pore diameter range of 0.01 ⁇ m to 10 ⁇ m is shaded.
  • the active material 100 containing the porous carbon-reduced silicate glass in the central portion 101 has a non-porous carbon-reduced It has physical properties different from those of the active material 100 containing silicate glass.
  • a peak MA (third peak) is detected in the pore distribution (solid line) for the active material 100 in which the central portion 101 contains porous carbon-reduced silicate glass.
  • This peak MA has an apex MAT within the pore diameter range of 0.01 ⁇ m to 10 ⁇ m.
  • FIG. 5 shows a case where the pore distribution (broken line) of the active material 100 containing non-porous carbon-reduced silicate glass is flat, but the pore distribution (broken line) is broad. (Upwardly convex gentle curved shape). Even in this case, no peak is detected.
  • the tendency described below is derived with respect to the analysis results (pore distribution) of the active material 100 using the mercury intrusion method.
  • a peak MA is detected because the core 101 containing the porous carbon-reduced silicate glass has a plurality of pores 103 .
  • the central portion 101 in which the central portion 101 contains non-porous carbon-reduced silicate glass, does not have the plurality of pores 103, and thus no peak is detected. Therefore, the active material 100 in which the central portion 101 contains porous carbon-reduced silicate glass has the above-described third physical properties related to the mercury intrusion method, and the central portion 101 contains non-porous carbon-reduced silicate glass. It has physical properties different from those of the active material 100 containing glass.
  • the tendency regarding the pore distribution (difference in physical properties) described here is not limited to the case where only the central portion 101 has a plurality of pores 103, and the central portion 101 and the covering portion 102 each have a plurality of pores. 103 is obtained in the same way.
  • the distribution of the rate of change in the amount of mercury intrusion (the horizontal axis is the hole diameter ( ⁇ m) and the vertical axis is is the rate of change in the intrusion amount of mercury).
  • a mercury porosimeter is used as the measuring device.
  • the pore size distribution corresponding to the apex MAT of the peak MA may be examined after the pore size distribution is measured.
  • the active material 100 is porous. Does not contain carbon-reduced silicate glass.
  • the reason why the active material 100 (central portion 101) containing the porous carbon-reduced silicate glass has the first physical property and the second physical property is that the reduction reaction proceeds more than the porous silicate glass.
  • the crystallinity of the glass material containing SiOx as a main component is optimized. This makes it easier for the active material 100 to sufficiently and stably store and release the electrode reactant, and also makes it easier for the active material 100 to continuously store and release the electrode reactant even if the electrode reactions are repeated.
  • a peak MA is detected in the pore distribution measured using the mercury intrusion method (third physical property).
  • the reason why the active material 100 containing porous carbon-reduced silicate glass has the third physical property is that when the central portion 101 (porous carbon-reduced silicate glass) expands and contracts during electrode reaction, a plurality of This is because the stress during expansion and contraction is relieved by utilizing the pores 103 of . As a result, the expansion and contraction of the central portion 101 is suppressed, so that the increase and decrease in the volume of the active material 100 as a whole is suppressed. Therefore, even if the electrode reaction is repeated, the state of the active material 100 is likely to be maintained, so that the active material 100 more stably absorbs and releases the electrode reactant.
  • the advantage of relaxing the stress during expansion and contraction by using a plurality of pores 103 in this way is not limited to the case where only the central portion 101 has a plurality of pores 103, and the central portion 101 and the covering portion The same is obtained when each of 102 has a plurality of pores 103 .
  • FIG. 6 shows a flow for explaining the manufacturing method of the active material 100. As shown in FIG. Note that the step numbers in parentheses described below correspond to the step numbers shown in FIG.
  • step S1 powdered porous silicate glass as a raw material is prepared (step S1).
  • the porous silicate glass that has already been synthesized may be obtained by purchasing or the like, or the porous silicate glass may be synthesized by oneself.
  • this porous silicate glass Since this porous silicate glass has not yet been subjected to carbon reduction treatment, it has almost the same structure as the porous carbon-reduced silicate glass, except that it does not have the above-described first physical properties and second physical properties. It has a configuration of That is, the porous silicate glass contains silicon, oxygen, the first element, the second element and the third element as constituent elements. Details of each of the first element, the second element and the third element are as described above.
  • silicon dioxide SiO 2
  • Conditions such as heating temperature and heating time can be arbitrarily set.
  • This supply source is a compound containing each constituent element.
  • the type of compound is not particularly limited, but specifically, it is an oxide of each constituent element. That is, sources of the first element include boron trioxide ( B2O5 ) and phosphorus pentoxide ( P2O5).
  • Sources of the second element are sodium oxide ( Na2O ), potassium oxide (K2O), scandium oxide (ScO), titanium oxide ( TiO2 ), zirconium oxide ( Zr2O ), and cerium oxide (CeO).
  • Sources of the third element include magnesium oxide (MgO), calcium oxide (CaO), strontium oxide (SrO) and barium oxide (BaO).
  • silicon dioxide and the supply sources of the first, second and third elements form a solid solution with each other. Therefore, a glass body containing silicon, oxygen, the first element, the second element, and the third element as constituent elements is formed, thereby synthesizing a porous silicate glass.
  • a mixture is obtained by mixing the porous silicate glass with a carbon source (step S2).
  • This carbon source is a general term for materials that can serve as carbon supply sources, and specifically includes one or both of carbon materials and carbonizable organic substances. That is, as the carbon source, only a carbon material may be used, only a carbonizable organic substance may be used, or both may be used.
  • Carbon materials include non-fibrous carbon and fibrous carbon.
  • Non-fibrous carbon includes carbon black
  • fibrous carbon includes carbon nanotubes and carbon nanofibers.
  • Organic substances that can be carbonized include sugars and polymer compounds.
  • Sugars include sucrose, maltose and cellulose.
  • Polymer compounds include polyimide, polyvinylidene fluoride, polymethyl methacrylate, polyvinylpyrrolidone, polyvinyl alcohol and polyacrylic acid. This is because the porous silicate glass is sufficiently reduced in the carbon reduction treatment. Also, as will be described later, the carbon source is used to easily and stably form the covering portion 102 having sufficient conductivity.
  • the mixture may be stirred using a stirring device.
  • Conditions such as stirring speed and stirring time can be arbitrarily set.
  • a paste-like mixture may be obtained by adding a binder, a solvent, and the like to the mixture.
  • a binder is not particularly limited, but specifically, one or more of polymer compounds such as polyvinylidene fluoride, polyimide, and polymethyl methacrylate.
  • the type of solvent is not particularly limited, but specifically, one or more of organic solvents such as N-methyl-2-pyrrolidone.
  • a binder solution in which a binder is previously dissolved in a solvent may be used.
  • the mixture is heated (step S3).
  • heating devices such as ovens are used.
  • Conditions such as heating temperature and heating time can be arbitrarily set. Specifically, the heating temperature is 700° C. to 1400° C., and the heating time is 1 hour to 20 hours.
  • the mixture When using a mixture containing a binder, the mixture may be heated in two stages. Specifically, the mixture is first dried by preheating the mixture.
  • the preheating conditions are not particularly limited, but specifically, the heating temperature is 40° C. to 500° C. and the heating time is 10 minutes to 3 hours. Subsequently, the dried mixture is pulverized. Finally, the pulverized mixture is heated.
  • the conditions for the main heating are not particularly limited, but specifically, the heating temperature is 700° C. to 1200° C. and the heating time is 1 hour to 20 hours.
  • the porous silicate glass is subjected to the carbon reduction treatment, so that the porous silicate glass is sufficiently reduced using the carbon source as a reducing agent. That is, since the crystalline state of SiO x is optimized so that the electrode reactant can be sufficiently occluded and desorbed, a porous carbon-reduced silicate glass containing SiO x as a main component is synthesized. Thus, a central portion 101 containing porous carbon-reduced silicate glass and having a plurality of pores 103 is formed.
  • carbon decomposed organic matter carbon adheres to the surface of the central portion 101 by utilizing the thermal decomposition of the carbon source used as the reducing agent.
  • a covering portion 102 is formed to cover the surface of the central portion 101 .
  • the presence or absence of the plurality of pores 103 in the covering portion 102 is determined according to the type of carbon source, as described above. Specifically, when a carbon material (non-fibrous carbon, fibrous carbon, etc.) is used as the carbon source, the covering portion 102 without the plurality of pores 103 is likely to be formed. Also, when a carbonizable organic substance (sugars, polymer compounds, etc.) is used as the carbon source, the covering portion 102 having a plurality of pores 103 is likely to be formed. Therefore, the presence or absence of the plurality of pores 103 in the covering portion 102 can be controlled according to the type of carbon source.
  • a carbon material non-fibrous carbon, fibrous carbon, etc.
  • a carbonizable organic substance sucgars, polymer compounds, etc.
  • the active material 100 including the central portion 101 and the covering portion 102 and having a plurality of pores 103 is manufactured (step S4).
  • the composition of the porous silicate glass used as the raw material is adjusted so that the content of each constituent element in all the constituent elements excluding oxygen and carbon satisfies the above conditions. do.
  • the content of silicon in all constituent elements excluding oxygen and carbon is 60 atomic % to 98 atomic %
  • the content of the first element in all constituent elements is 1 atomic % to 25 atomic %
  • the content of the second element in all the constituent elements is 1 atomic % to 34 atomic %
  • the content of the third element in all the constituent elements is 0 atomic % to 6 atomic %.
  • the active material 100 central portion 101 containing porous carbon-reduced silicate glass manufactured using carbon reduction treatment
  • the physical properties of the porous silicate glass change due to the carbon reduction treatment.
  • a first physical property and a second physical property are obtained.
  • the structure of the porous silicate glass is the porous carbon-reduced silicate glass. (the structure of the central portion 101), the above-described third physical property is obtained.
  • Active material 100 includes porous carbon-reduced silicate glass.
  • the active material 100 contains silicon, oxygen, the first element, the second element, and the third element as constituent elements, and each of the constituent elements excluding oxygen and carbon The content of the constituent elements satisfies the above conditions.
  • a peak XA having an apex XAT and a shoulder XAS is detected (first physical property).
  • a peak RA having an apex RAT is detected in the analysis result (Raman spectrum) of the active material 100 measured using Raman spectroscopy (second physical property).
  • a peak MA having an apex MAT is detected in the analysis result (pore size distribution) of the active material 100 measured using the mercury intrusion method (third physical property).
  • the reduction reaction of the porous silicate glass proceeds sufficiently, so that the glass containing SiO x as a main component
  • the crystallinity of the material is optimized. Therefore, the active material 100 tends to sufficiently and stably absorb and release the electrode reactant, and the active material 100 tends to continuously absorb and release the electrode reactant even if the electrode reaction is repeated.
  • the central portion 101 contains the carbon-reduced silicic acid compound having the first physical property and the second physical property. and excellent swelling properties can be obtained.
  • the peak XA is decomposed into five types of Si-derived peaks (Si 0 peak, Si 1+ peak, Si 2+ peak, Si 3+ peak and Si 4+ peak), the area ratio S2/S1 is 0.5. Even when it is 85 or more, excellent charge/discharge characteristics and excellent swollenness characteristics can be obtained for the same reason.
  • the active material 100 includes the central portion 101 and the covering portion 102 , the surface of the central portion 101 containing the porous carbon-reduced silicate glass is covered with the conductive covering portion 102 . Therefore, since the electron conductivity of the active material 100 is improved, a higher effect can be obtained.
  • the central portion 101 has a plurality of pores 103, an increase or decrease in the volume of the entire active material 100 is sufficiently suppressed, so that a higher effect can be obtained. Moreover, if each of the central portion 101 and the coating portion 102 has a plurality of pores 103, the volume of the active material 100 as a whole is further suppressed, so that a significantly high effect can be obtained.
  • the active material 100 containing SiO x as the main component in order to manufacture the active material 100 containing SiO x as the main component, only simple and inexpensive processes such as mixing and heat treatment may be used. There is no need to use complicated and expensive processes such as vapor deposition. Therefore, the active material 100 can be manufactured easily and stably at low cost.
  • the carbon source contains a carbon material or the like
  • the porous silicate glass is sufficiently reduced in the carbon reduction treatment, and the covering portion 102 having sufficient conductivity is easily and stably formed. A higher effect can be obtained.
  • Electrode and secondary battery> a secondary battery according to an embodiment of the present technology, which is an application example of the active material described above, will be described.
  • the electrode of one embodiment of the present technology is a part (one component) of the secondary battery, the electrode will be described together below.
  • the active material described above is used as the negative electrode active material, the case where the active material is used for the negative electrode will be described below.
  • the secondary battery described here is a secondary battery in which battery capacity is obtained by utilizing the absorption and release of electrode reactants, and includes an electrolytic solution together with a positive electrode and a negative electrode.
  • the charge capacity of the negative electrode is larger than the discharge capacity of the positive electrode. That is, the electrochemical capacity per unit area of the negative electrode is set to be larger than the electrochemical capacity per unit area of the positive electrode. This is to prevent electrode reactants from depositing on the surface of the negative electrode during charging.
  • a secondary battery that utilizes intercalation and deintercalation of lithium, which is an electrode reactant, is a so-called lithium ion secondary battery.
  • FIG. 7 shows a perspective configuration of a secondary battery.
  • FIG. 8 shows a cross-sectional configuration of the battery element 20 shown in FIG.
  • FIG. 9 shows the planar configuration of each of the positive electrode 21 and the negative electrode 22 shown in FIG.
  • FIG. 7 shows the state in which the exterior film 10 and the battery element 20 are separated from each other, and the cross section of the battery element 20 along the XZ plane is indicated by a broken line.
  • FIG. 8 only part of the battery element 20 is shown.
  • FIG. 9 shows a state in which the positive electrode 21 and the negative electrode 22 are separated from each other.
  • This secondary battery as shown in FIGS. 7 to 9, includes an exterior film 10, a battery element 20, a positive electrode lead 31, a negative electrode lead 32, and sealing films 41 and .
  • the secondary battery described here is a laminated film type secondary battery using a flexible (or flexible) exterior film 10 .
  • the exterior film 10 is a flexible exterior member that houses the battery element 20, and has a sealed bag-like structure with the battery element 20 housed inside. is doing. Therefore, the exterior film 10 accommodates the electrolytic solution together with the positive electrode 21 and the negative electrode 22, which will be described later.
  • the exterior film 10 is a single film-like member and is folded in the folding direction F.
  • the exterior film 10 is provided with a recessed portion 10U (so-called deep drawn portion) for housing the battery element 20 .
  • the exterior film 10 is a three-layer laminate film in which a fusion layer, a metal layer, and a surface protection layer are laminated in this order from the inside. Outer peripheral edge portions of the fusion layer are fused together.
  • the fusible layer contains a polymer compound such as polypropylene.
  • the metal layer contains a metal material such as aluminum.
  • the surface protective layer contains a polymer compound such as nylon.
  • the configuration (number of layers) of the exterior film 10 is not particularly limited, and may be one layer, two layers, or four layers or more.
  • the sealing film 41 is inserted between the exterior film 10 and the positive electrode lead 31
  • the sealing film 42 is inserted between the exterior film 10 and the negative electrode lead 32 .
  • one or both of the sealing films 41 and 42 may be omitted.
  • the sealing film 41 is a sealing member that prevents outside air from entering the exterior film 10 . Further, the sealing film 41 contains a polymer compound such as polyolefin having adhesiveness to the positive electrode lead 31, and the polyolefin is polypropylene or the like.
  • the structure of the sealing film 42 is the same as the structure of the sealing film 41 except that it is a sealing member having adhesion to the negative electrode lead 32 . That is, the sealing film 42 contains a high molecular compound such as polyolefin having adhesiveness to the negative electrode lead 32 .
  • the battery element 20 is a power generation element including a positive electrode 21, a negative electrode 22, a separator 23, and an electrolytic solution (not shown), as shown in FIGS. It is
  • This battery element 20 is a so-called wound electrode assembly. That is, in the battery element 20, the positive electrode 21 and the negative electrode 22 are stacked with the separator 23 interposed therebetween, and the positive electrode 21, the negative electrode 22, and the separator are stacked around the winding axis P, which is a virtual axis extending in the Y-axis direction. 23 is wound. Thus, the positive electrode 21 and the negative electrode 22 are wound while facing each other with the separator 23 interposed therebetween.
  • the three-dimensional shape of the battery element 20 is not particularly limited.
  • the cross section of the battery element 20 intersecting the winding axis P (the cross section along the XZ plane) has a flat shape defined by the long axis J1 and the short axis J2. have.
  • the major axis J1 is a virtual axis that extends in the X-axis direction and has a length greater than that of the minor axis J2.
  • the cross-sectional shape of the battery element 20 is a flat, substantially elliptical shape.
  • the positive electrode 21 includes a positive electrode current collector 21A and a positive electrode active material layer 21B, as shown in FIGS.
  • the positive electrode current collector 21A has a pair of surfaces on which the positive electrode active material layer 21B is provided.
  • This positive electrode current collector 21A contains a conductive material such as a metal material, and the metal material is aluminum or the like.
  • the positive electrode active material layer 21B is provided on both sides of the positive electrode current collector 21A, and contains one or more of positive electrode active materials capable of intercalating and deintercalating lithium.
  • the positive electrode active material layer 21B may be provided only on one side of the positive electrode current collector 21A on the side where the positive electrode 21 faces the negative electrode 22 .
  • the positive electrode active material layer 21B may further contain one or more of other materials such as a positive electrode binder and a positive electrode conductive agent.
  • a method for forming the positive electrode active material layer 21B is not particularly limited, but specifically, one or more of coating methods and the like are used.
  • the type of positive electrode active material is not particularly limited, it is specifically a lithium-containing compound.
  • This lithium-containing compound is a compound containing lithium and one or more transition metal elements as constituent elements, and may further contain one or more other elements as constituent elements.
  • the type of the other element is not particularly limited as long as it is an element other than lithium and transition metal elements, but specifically, it is an element belonging to Groups 2 to 15 in the long period periodic table.
  • the type of lithium-containing compound is not particularly limited, but specific examples include oxides, phosphoric acid compounds, silicic acid compounds and boric acid compounds.
  • oxides include LiNiO2 , LiCoO2 , LiCo0.98Al0.01Mg0.01O2 , LiNi0.5Co0.2Mn0.3O2 , LiNi0.8Co0.15Al0.05O2 , LiNi0.33Co0.33Mn0.33Mn0.33O2 .
  • 1.2Mn0.52Co0.175Ni0.1O2 Li1.15 ( Mn0.65Ni0.22Co0.13 ) O2 and LiMn2O4 .
  • _ _ Specific examples of phosphoric acid compounds include LiFePO4 , LiMnPO4 , LiFe0.5Mn0.5PO4 and LiFe0.3Mn0.7PO4 .
  • the positive electrode binder contains one or more of synthetic rubber and polymer compounds.
  • Synthetic rubbers include styrene-butadiene-based rubber, fluorine-based rubber, and ethylene propylene diene.
  • Polymer compounds include polyvinylidene fluoride, polyimide and carboxymethyl cellulose.
  • the positive electrode conductive agent contains one or more of conductive materials such as carbon materials, and the carbon materials include graphite, carbon black, acetylene black, and ketjen black.
  • the conductive material may be a metal material, a polymer compound, or the like.
  • the positive electrode active material layer 21B is provided only on part of the positive electrode current collector 21A. Therefore, the portion of the positive electrode current collector 21A where the positive electrode active material layer 21B is not provided is exposed without being covered with the positive electrode active material layer 21B.
  • the positive electrode current collector 21A extends in the longitudinal direction (X-axis direction) and includes a covered portion 21AX and a pair of uncovered portions 21AY.
  • the covering portion 21AX is located in the central portion of the positive electrode current collector 21A in the longitudinal direction, and is the portion where the positive electrode active material layer 21B is formed.
  • the pair of uncovered portions 21AY are located at both ends of the positive electrode current collector 21A in the longitudinal direction, and are portions where the positive electrode active material layer 21B is not formed.
  • the covered portion 21AX is covered with the positive electrode active material layer 21B, whereas the pair of uncovered portions 21AY are exposed without being covered with the positive electrode active material layer 21B.
  • the positive electrode active material layer 21B is lightly shaded.
  • the negative electrode 22 includes a negative electrode current collector 22A and a negative electrode active material layer 22B, as shown in FIGS.
  • the negative electrode current collector 22A has a pair of surfaces on which the negative electrode active material layer 22B is provided.
  • This negative electrode current collector 22A contains a conductive material such as a metal material, and the metal material is copper or the like.
  • the negative electrode active material layer 22B is provided on both surfaces of the negative electrode current collector 22A, and contains one or more of negative electrode active materials capable of intercalating and deintercalating lithium.
  • the structure of this negative electrode active material is the same as the structure of the active material described above.
  • the negative electrode active material layer 22B may be provided only on one side of the negative electrode current collector 22A on the side where the negative electrode 22 faces the positive electrode 21 .
  • the negative electrode active material layer 22B may further contain one or more of other materials such as a negative electrode binder and a negative electrode conductor.
  • the method of forming the negative electrode active material layer 22B is not particularly limited, but specifically, any one of a coating method, a vapor phase method, a liquid phase method, a thermal spraying method, a firing method (sintering method), or the like, or Two or more types.
  • the negative electrode active material layer 22B may further contain other negative electrode active materials.
  • the type of other negative electrode active material is not particularly limited, but specifically includes one or both of a carbon material and a metal-based material. This is because a high energy density can be obtained.
  • Carbon materials include graphitizable carbon, non-graphitizable carbon and graphite (natural graphite and artificial graphite).
  • a metallic material is a material containing as constituent elements one or more of metallic elements and semi-metallic elements capable of forming an alloy with lithium. , one or both of silicon and tin, and the like. This metallic material may be a single substance, an alloy, a compound, a mixture of two or more of them, or a material containing two or more of these phases. Specific examples of metallic materials include TiSi 2 and SiO x (0 ⁇ x ⁇ 2, or 0.2 ⁇ x ⁇ 1.4).
  • each of the negative electrode binder and the negative electrode conductive agent is the same as those of the positive electrode binder and the positive electrode conductive agent.
  • the negative electrode active material layer 22B is provided on the entire negative electrode current collector 22A. Therefore, the entire negative electrode current collector 22A is covered with the negative electrode active material layer 22B without being exposed.
  • the negative electrode current collector 22A extends in the longitudinal direction (X-axis direction), and the negative electrode active material layer 22B includes a pair of non-facing portions 22BZ.
  • the pair of non-facing portions 22BZ are portions that face the pair of non-coated portions 21AY. That is, the pair of non-opposing portions 22BZ are portions that do not face the positive electrode active material layer 21B, and thus do not participate in the charge/discharge reaction.
  • the negative electrode active material layer 22B is shaded.
  • the negative electrode active material layer 22B is provided entirely on both surfaces of the negative electrode current collector 22A, whereas the positive electrode active material layer 21B is provided only on part of both surfaces of the positive electrode current collector 21A (coating portion 21AX). This is to prevent lithium released from the positive electrode active material layer 21B from depositing on the surface of the negative electrode 22 during charging.
  • the negative electrode active material for analysis it is preferable to use the non-facing portion 22BZ as the negative electrode active material layer 22B for collecting the . Since the non-facing portion 22BZ hardly participates in the charge-discharge reaction, the state (composition, physical properties, etc.) of the negative electrode active material (porous carbon-reduced silicate glass) is not affected by the charge-discharge reaction, and the negative electrode 22 is formed at the time of formation. This is because it is easy to maintain. As a result, it is possible to stably and reproducibly check whether the three types of physical properties are obtained even when the secondary battery has been used.
  • the separator 23 is an insulating porous film interposed between the positive electrode 21 and the negative electrode 22, as shown in FIG. Allows lithium ions to pass through.
  • This separator 23 contains a polymer compound such as polyethylene.
  • the electrolyte contains a solvent and an electrolyte salt, and impregnates each of the positive electrode 21 , the negative electrode 22 and the separator 23 .
  • the solvent contains one or more of non-aqueous solvents (organic solvents), and the electrolytic solution containing the non-aqueous solvent is the so-called non-aqueous electrolytic solution.
  • non-aqueous solvents include esters, ethers, and the like, and more specifically, carbonate compounds, carboxylic acid ester compounds, lactone compounds, and the like.
  • the carbonate compounds include cyclic carbonates and chain carbonates.
  • Cyclic carbonates include ethylene carbonate and propylene carbonate
  • chain carbonates include dimethyl carbonate, diethyl carbonate and methylethyl carbonate.
  • Carboxylic acid ester compounds include ethyl acetate, ethyl propionate and ethyl trimethylacetate.
  • Lactone compounds include ⁇ -butyrolactone and ⁇ -valerolactone.
  • Ethers include 1,2-dimethoxyethane, tetrahydrofuran, 1,3-dioxolane and 1,4-dioxane, in addition to the above-mentioned lactone compounds.
  • non-aqueous solvents include unsaturated cyclic carbonates, halogenated carbonates, sulfonic acid esters, phosphoric acid esters, acid anhydrides, nitrile compounds and isocyanate compounds. This is because the chemical stability of the electrolytic solution is improved.
  • unsaturated cyclic carbonates include vinylene carbonate, vinylethylene carbonate, and methyleneethylene carbonate.
  • Halogenated carbonates include ethylene fluorocarbonate and ethylene difluorocarbonate.
  • Sulfonic acid esters include propane sultone and propene sultone.
  • Phosphate esters include trimethyl phosphate.
  • Acid anhydrides include cyclic carboxylic anhydrides, cyclic disulfonic anhydrides and cyclic carboxylic sulfonic anhydrides.
  • Cyclic carboxylic anhydrides include succinic anhydride, glutaric anhydride and maleic anhydride.
  • Cyclic disulfonic anhydrides include ethanedisulfonic anhydride and propanedisulfonic anhydride.
  • Cyclic carboxylic sulfonic anhydrides include sulfobenzoic anhydride, sulfopropionic anhydride and sulfobutyric anhydride.
  • Nitrile compounds include acetonitrile and succinonitrile.
  • the isocyanate compound is hexamethylene diisocyanate and the like.
  • the electrolyte salt contains one or more of light metal salts such as lithium salts.
  • This lithium salt includes lithium hexafluorophosphate (LiPF 6 ), lithium tetrafluoroborate (LiBF 4 ), lithium trifluoromethanesulfonate (LiCF 3 SO 3 ), lithium bis(fluorosulfonyl)imide (LiN(FSO 2 ) 2 ), lithium bis(trifluoromethanesulfonyl)imide (LiN( CF3SO2 ) 2 ) , lithium tris(trifluoromethanesulfonyl)methide (LiC(CF3SO2)3 ) and lithium bis(oxalato)borate (LiB(C 2 O 4 ) 2 ) and the like.
  • the content of the electrolyte salt is not particularly limited, but is 0.3 mol/kg to 3.0 mol/kg with respect to the solvent. This is because high ionic conductivity can be obtained
  • the positive lead 31 is a positive terminal connected to the positive electrode 21, and more specifically connected to the positive current collector 21A.
  • the positive electrode lead 31 extends from the inside of the exterior film 10 to the outside, and contains a conductive material such as aluminum.
  • the shape of the positive electrode lead 31 is not particularly limited, but specifically, it is either a thin plate shape, a mesh shape, or the like.
  • the negative electrode lead 32 is a negative electrode terminal connected to the negative electrode 22, as shown in FIG. 7, and more specifically connected to the negative electrode current collector 22A.
  • the negative electrode lead 32 is led out from the interior of the exterior film 10 and contains a conductive material such as copper.
  • the lead-out direction of the negative lead 32 is the same as the lead-out direction of the positive lead 31 .
  • Details regarding the shape of the negative electrode lead 32 are the same as those regarding the shape of the positive electrode lead 31 .
  • a paste-like positive electrode mixture slurry is prepared by putting a mixture (positive electrode mixture) in which a positive electrode active material, a positive electrode binder, a positive electrode conductor, and the like are mixed together into a solvent.
  • This solvent may be an aqueous solvent or an organic solvent.
  • the cathode active material layer 21B is formed by applying the cathode mixture slurry to both surfaces of the cathode current collector 21A.
  • the cathode active material layer 21B may be compression-molded using a roll press machine or the like. In this case, the positive electrode active material layer 21B may be heated, or compression molding may be repeated multiple times. As a result, the cathode active material layers 21B are formed on both surfaces of the cathode current collector 21A, so that the cathode 21 is produced.
  • a negative electrode 22 is formed by the same procedure as that of the positive electrode 21 described above. Specifically, first, a paste-like negative electrode mixture slurry is prepared by putting a mixture (negative electrode mixture) in which a negative electrode active material, a negative electrode binder, a negative electrode conductor, and the like are mixed together into a solvent. . Subsequently, the anode active material layer 22B is formed by applying the anode mixture slurry to both surfaces of the anode current collector 22A. After that, the negative electrode active material layer 22B may be compression molded. As a result, the negative electrode 22 is manufactured because the negative electrode active material layers 22B are formed on both surfaces of the negative electrode current collector 22A.
  • This solvent may be an aqueous solvent or an organic solvent. This disperses or dissolves the electrolyte salt in the solvent, thus preparing an electrolytic solution.
  • the positive electrode lead 31 is connected to the positive electrode current collector 21A of the positive electrode 21 by welding or the like, and the negative electrode lead 32 is connected to the negative electrode current collector 22A of the negative electrode 22 by welding or the like.
  • the positive electrode 21 and the negative electrode 22 are laminated with the separator 23 interposed therebetween, and then the positive electrode 21, the negative electrode 22 and the separator 23 are wound to form a wound body.
  • This wound body has the same structure as the battery element 20 except that the positive electrode 21, the negative electrode 22 and the separator 23 are not impregnated with the electrolytic solution. Subsequently, by pressing the wound body using a pressing machine or the like, the wound body is formed into a flat shape.
  • the exterior films 10 (bonding layer/metal layer/surface protective layer) are folded to face each other. Subsequently, by using a heat-sealing method or the like to join the outer peripheral edges of two sides of the mutually facing exterior films 10 (fusion layer) to each other, it is wound inside the bag-shaped exterior film 10. Store the revolving body.
  • the outer peripheral edges of the remaining one side of the exterior film 10 are joined together using a heat sealing method or the like.
  • a sealing film 41 is inserted between the packaging film 10 and the positive electrode lead 31 and a sealing film 42 is inserted between the packaging film 10 and the negative electrode lead 32 .
  • the wound body is impregnated with the electrolytic solution, so that the battery element 20 is produced, and the battery element 20 is sealed inside the bag-shaped exterior film 10, so that the secondary battery is assembled.
  • the secondary battery after assembly is charged and discharged.
  • Various conditions such as environmental temperature, number of charge/discharge times (number of cycles), and charge/discharge conditions can be arbitrarily set.
  • films are formed on the respective surfaces of the positive electrode 21 and the negative electrode 22, so that the state of the secondary battery is electrochemically stabilized.
  • a laminated film type secondary battery using the exterior film 10 is completed.
  • the negative electrode active material of the negative electrode 22 has the same structure as the active material described above.
  • the negative electrode active material can absorb and release lithium sufficiently and stably, and expansion and contraction of the negative electrode active material can be suppressed even if the charge and discharge reactions are repeated. facilitates continuous absorption and release of lithium. Therefore, excellent charge/discharge characteristics and excellent swelling characteristics can be obtained.
  • the secondary battery is a lithium-ion secondary battery
  • a sufficient battery capacity can be stably obtained by utilizing the absorption and release of lithium, so a higher effect can be obtained.
  • the active material 100 has a central portion 101 as well as a covering portion 102 .
  • active material 100 may include only central portion 101 and may not include covering portion 102 .
  • covering portion 102 may be removed. Also in this case, since the electrode reactant can be absorbed and discharged in the active material 100 (central portion 101), a similar effect can be obtained.
  • the active material 100 preferably includes the covering portion 102 as well as the central portion 101 .
  • a separator 23 which is a porous membrane, was used. However, although not specifically illustrated here, a laminated separator including a polymer compound layer may be used.
  • a laminated separator includes a porous membrane having a pair of surfaces and a polymer compound layer disposed on one or both sides of the porous membrane. This is because the adhesiveness of the separator to each of the positive electrode 21 and the negative electrode 22 is improved, so that positional deviation (winding deviation) of the battery element 20 is suppressed. As a result, swelling of the secondary battery is suppressed even if a decomposition reaction or the like of the electrolytic solution occurs.
  • the polymer compound layer contains a polymer compound such as polyvinylidene fluoride. This is because polyvinylidene fluoride or the like has excellent physical strength and is electrochemically stable.
  • One or both of the porous film and the polymer compound layer may contain one or more of a plurality of insulating particles. This is because the plurality of insulating particles dissipate heat when the secondary battery generates heat, thereby improving the safety (heat resistance) of the secondary battery.
  • the insulating particles contain one or more of insulating materials such as inorganic materials and resin materials. Specific examples of inorganic materials are aluminum oxide, aluminum nitride, boehmite, silicon oxide, titanium oxide, magnesium oxide and zirconium oxide. Specific examples of resin materials include acrylic resins and styrene resins.
  • the precursor solution is applied to one or both sides of the porous membrane.
  • a plurality of insulating particles may be added to the precursor solution.
  • the positive electrode 21 and the negative electrode 22 are laminated with the separator 23 and the electrolyte layer interposed therebetween, and the positive electrode 21, the negative electrode 22, the separator 23 and the electrolyte layer are wound.
  • This electrolyte layer is interposed between the positive electrode 21 and the separator 23 and interposed between the negative electrode 22 and the separator 23 .
  • the electrolyte layer contains a polymer compound together with an electrolytic solution, and the electrolytic solution is held by the polymer compound. This is because leakage of the electrolytic solution is prevented.
  • the composition of the electrolytic solution is as described above.
  • Polymer compounds include polyvinylidene fluoride and the like.
  • the secondary battery has one positive electrode lead 31 .
  • the secondary battery may have two or more positive electrode leads 31 .
  • the positive electrode lead 31 can be used to enable the secondary battery to conduct electricity, so that similar effects can be obtained.
  • the electric resistance of the battery element 20 decreases, so that a higher effect can be obtained.
  • the number of positive leads 31 described here is the same for the number of negative leads 32 . That is, although the secondary battery has one negative electrode lead 32 in FIG. 7 , the secondary battery may have two or more negative electrode leads 32 . In this case as well, the negative electrode lead 32 can be used to enable the secondary battery to conduct electricity, so that similar effects can be obtained. In particular, when the number of negative electrode leads 32 is increased, the electric resistance of the battery element 20 is decreased, so that a higher effect can be obtained.
  • a secondary battery used as a power source may be a main power source for electronic devices and electric vehicles, or may be an auxiliary power source.
  • a main power source is a power source that is preferentially used regardless of the presence or absence of other power sources.
  • An auxiliary power supply is a power supply that is used in place of the main power supply or that is switched from the main power supply.
  • Secondary battery applications are as follows. Electronic devices such as video cameras, digital still cameras, mobile phones, laptop computers, headphone stereos, portable radios and portable information terminals. Backup power and storage devices such as memory cards. Power tools such as power drills and power saws. It is a battery pack mounted on an electronic device. Medical electronic devices such as pacemakers and hearing aids. It is an electric vehicle such as an electric vehicle (including a hybrid vehicle). It is a power storage system such as a home or industrial battery system that stores power in preparation for emergencies. In these uses, one secondary battery may be used, or a plurality of secondary batteries may be used.
  • the battery pack may use a single cell or an assembled battery.
  • An electric vehicle is a vehicle that operates (runs) using a secondary battery as a drive power source, and may be a hybrid vehicle that also includes a drive source other than the secondary battery.
  • electric power stored in a secondary battery which is an electric power storage source, can be used to use electric appliances for home use.
  • FIG. 10 shows the block configuration of the battery pack.
  • the battery pack described here is a battery pack (a so-called soft pack) using one secondary battery, and is mounted in an electronic device such as a smart phone.
  • This battery pack includes a power supply 51 and a circuit board 52, as shown in FIG.
  • This circuit board 52 is connected to the power supply 51 and includes a positive terminal 53 , a negative terminal 54 and a temperature detection terminal 55 .
  • the power supply 51 includes one secondary battery.
  • the positive lead is connected to the positive terminal 53 and the negative lead is connected to the negative terminal 54 .
  • the power supply 51 can be connected to the outside through the positive terminal 53 and the negative terminal 54, and thus can be charged and discharged.
  • the circuit board 52 includes a control section 56 , a switch 57 , a thermal resistance element (PTC element) 58 and a temperature detection section 59 .
  • the PTC element 58 may be omitted.
  • the control unit 56 includes a central processing unit (CPU), memory, etc., and controls the operation of the entire battery pack. This control unit 56 detects and controls the use state of the power source 51 as necessary.
  • CPU central processing unit
  • memory etc.
  • the overcharge detection voltage is not particularly limited, but is specifically 4.2V ⁇ 0.05V, and the overdischarge detection voltage is not particularly limited, but is specifically 2.4V ⁇ 0.1V. is.
  • the switch 57 includes a charge control switch, a discharge control switch, a charge diode, a discharge diode, and the like, and switches connection/disconnection between the power supply 51 and an external device according to instructions from the control unit 56 .
  • the switch 57 includes a field effect transistor (MOSFET) using a metal oxide semiconductor, etc., and the charge/discharge current is detected based on the ON resistance of the switch 57 .
  • MOSFET field effect transistor
  • the temperature detection unit 59 includes a temperature detection element such as a thermistor, measures the temperature of the power supply 51 using the temperature detection terminal 55 , and outputs the temperature measurement result to the control unit 56 .
  • the measurement result of the temperature measured by the temperature detection unit 59 is used when the control unit 56 performs charging/discharging control at the time of abnormal heat generation and when the control unit 56 performs correction processing when calculating the remaining capacity.
  • FIG. 11 shows a cross-sectional configuration of a test secondary battery (coin type).
  • a negative electrode active material was produced
  • a coin-type secondary battery was produced using the negative electrode active material
  • battery characteristics of the secondary battery were evaluated.
  • the test electrode 201 is accommodated inside the exterior cup 204 and the counter electrode 203 is accommodated inside the exterior can 202 .
  • the test electrode 201 and the counter electrode 203 are stacked together with the separator 205 interposed therebetween, and the outer can 202 and the outer cup 204 are crimped together with the gasket 206 interposed therebetween.
  • Each of the test electrode 201, the counter electrode 203 and the separator 205 is impregnated with the electrolytic solution.
  • porous silicate glass as a raw material was prepared.
  • the types of constituent elements (excluding oxygen and carbon) and the content (atomic %) of each constituent element regarding the porous carbon-reduced silicate glass synthesized using this porous silicate glass are shown in Tables 1 and 2. is as shown in
  • each constituent element was calculated based on the analysis results of the porous carbon-reduced silicate glass using SEM-EDX, as described above.
  • the lithium detection sensitivity is extremely low, so the lithium content is so small that it hardly affects the content of the second element. Therefore, in Tables 1 and 2, the description of the lithium content is omitted.
  • a mixture was obtained by mixing porous silicate glass with a carbon source.
  • a carbon source carbon black (Examples 1 to 6 and Comparative Examples 1 to 8), which is a carbon material, and polyimide (Example 7) and sucrose (Example 8), which are carbonizable organic substances, were used. .
  • the amount of binder solution added to the mixture was 10% by weight (solid content ratio).
  • the porous carbon-reduced silicate glass was synthesized by reducing the porous carbon-reduced silicate glass in the presence of the carbon source (carbon reduction treatment), the porous carbon-reduced silicate glass is included. A center was formed.
  • decomposition products of the carbon source (organic decomposed carbon) adhered to the surface of the central portion a coated portion was formed. As a result, a flaky negative electrode active material including a central portion and a covering portion was obtained.
  • the flake-shaped negative electrode active material was pulverized using a mortar to obtain a powdered negative electrode active material, and then the powdered negative electrode active material was sieved using a mesh (53 ⁇ m).
  • SEM scanning electron microscope
  • Table 2 shows the results of analyzing the negative electrode active material using XPS.
  • the position of the vertex XAT (binding energy: eV) the presence or absence of the shoulder XAS, and The half width (eV) of peak XA and the area ratio S2/S1 were examined.
  • Table 2 shows the results of analyzing the negative electrode active material using Raman spectroscopy.
  • the position of the apex RAT (Raman shift: cm ⁇ 1 ) was examined based on the analysis results of the negative electrode active material (Raman spectrum shown in FIG. 4) according to the procedure described above.
  • the analysis results of the negative electrode active material (pore distribution shown in FIG. 5) showed a peak having an apex MAT within a range of pore diameters of 0.01 ⁇ m to 10 ⁇ m. MA was detected.
  • a test electrode 201 was produced and an electrolytic solution was prepared according to the procedure described below, and then a coin-type secondary battery was produced using the test electrode 201, the electrolytic solution, and the like.
  • a negative electrode was produced as the test electrode 201 .
  • the negative electrode active material described above, a negative electrode binder precursor (polyamic acid solution (polyimide precursor) U-varnish-A manufactured by Ube Industries, Ltd.), and two types of negative electrode conductors (manufactured by TIMCAL Carbon powder KS6 and acetylene black (Denka Black (registered trademark) manufactured by Denka Co., Ltd.) were mixed with each other to prepare a negative electrode mixture.
  • the negative electrode mixture was added to a solvent (N-methyl-2-pyrrolidone, which is an organic solvent), and the solvent was stirred to prepare a pasty negative electrode mixture slurry.
  • a negative electrode binder polyimide
  • a negative electrode active material layer containing the negative electrode active material, the negative electrode binder, and the negative electrode conductor was formed.
  • a test electrode 201 which is a negative electrode, was produced.
  • a test electrode 201 was prepared by the same procedure except that another negative electrode active material (silicon monoxide (SiO)) was used instead of the above negative electrode active material (Comparative Example 8 ).
  • SiO silicon monoxide
  • a lithium metal plate was used as the counter electrode 203 .
  • test electrode 201 was accommodated inside the outer cup 204 and the counter electrode 203 was accommodated inside the outer can 202 .
  • a separator 205 (a microporous polyethylene film having a thickness of 5 ⁇ m) impregnated with an electrolytic solution is interposed between the test electrode 201 housed inside the exterior cup 204 and the interior of the exterior can 202 .
  • the counter electrode 203 are stacked on each other.
  • the test electrode 201 and the counter electrode 203 were partially impregnated with the electrolytic solution impregnated in the separator 205 .
  • the outer can 202 and the outer cup 204 were crimped together with the gasket 206 interposed therebetween.
  • the test electrode 201, the counter electrode 203, the separator 205, and the electrolytic solution were enclosed by the outer can 202 and the outer cup 204, thereby assembling a coin-type secondary battery.
  • constant-current charging was performed at a current of 0.1C until the voltage reached 4.2V
  • constant-voltage charging was performed at the voltage of 4.2V until the current reached 0.05C.
  • constant current discharge was performed at a current of 0.1C until the voltage reached 2.5V.
  • 0.1C is a current value that can completely discharge the battery capacity (theoretical capacity) in 10 hours
  • 0.05C is a current value that completely discharges the battery capacity in 20 hours.
  • the discharge capacity (mAh) of the first cycle was measured by discharging the charged secondary battery in the same environment.
  • the discharge capacity per unit weight (mAh/g) which is an index for evaluating discharge characteristics, was calculated based on the weight (g) of the negative electrode active material.
  • capacity retention rate (discharge capacity at 100th cycle/discharge capacity at 1st cycle) x 100. .
  • the charging/discharging conditions were the same as the charging/discharging conditions during stabilization of the secondary battery.
  • the following conditions are satisfied with respect to the composition of the negative electrode active material, and the following conditions are satisfied with respect to the analysis results of the negative electrode active material using XPS and Raman spectroscopy (XPS spectrum and Raman spectrum of Si2p): is satisfied (Examples 1 to 8), compared to the case where those conditions are not satisfied (Comparative Examples 1 to 7), regardless of the type of carbon source, a high charge capacity And while a high discharge capacity was obtained, a high capacity retention rate was also obtained.
  • the negative electrode active material contains silicon, oxygen, the first element, the second element and the third element as constituent elements.
  • the content of silicon in all constituent elements is 60 atomic % to 98 atomic %
  • the content of the first element in all constituent elements is 1 atomic % to 25 atomic %
  • the entire composition The content of the second element in the elements is 1 atomic % to 34 atomic %
  • the content of the third element in all constituent elements is 0 atomic % to 6 atomic %.
  • Conditions for analysis results of the negative electrode active material In the XPS spectrum (Si2p) measured using XPS, a peak XA having an apex XAT and a shoulder XAS shown in FIG. (first physical property). In addition, in the Raman spectrum measured using Raman spectroscopy, a peak RA having an apex RAT shown in FIG. (second physical property).
  • the half-value width is 4.0 eV or more, or the area
  • the ratio S2/S1 was 0.85 or more, sufficient charge capacity and sufficient discharge capacity were obtained, and a high capacity retention rate was obtained.
  • the charge capacity and the discharge capacity are higher than when other negative electrode active materials are used. Diminished. However, each of the charge capacity and discharge capacity was sufficiently high within an acceptable range.
  • the capacity retention rate was significantly increased compared to the case of using other negative electrode active materials.
  • Examples 9 and 10 and Comparative Examples 9 and 10> As shown in Table 3, two types of diatomaceous earths (diatomaceous earths 1 and 2), which are porous silicate glasses that satisfy the conditions regarding the composition and analysis results described above, were used as raw materials to produce porous carbon-reduced silicate glasses. A secondary battery was produced by the same procedure except that the was synthesized, and then the battery characteristics of the secondary battery were evaluated. In this case, polyimide was used as the carbon source.
  • the position of the apex MAT of the peak MA ( The pore diameter ( ⁇ m)) is as shown in Table 3.
  • non-porous silicate glasses 1 and 2 that satisfy the conditions regarding the composition and analysis results described above were used as raw materials to form non-porous glass.
  • a secondary battery was produced by the same procedure except that the carbon-reduced silicate glass was formed, and then the battery characteristics of the secondary battery were evaluated.
  • silicate glass 1 is similar to that of diatomaceous earth 1, except that it does not have a plurality of pores.
  • Table 3 shows the analysis results (pore distribution shown in FIG. 5) of the negative electrode active material containing non-porous carbon-reduced silicate glass formed using non-porous silicate glass.
  • the swelling characteristics were evaluated along with the charging characteristics (charge capacity (mAh/g)) described above.
  • the thickness of the negative electrode active material layer was measured using a laser thickness gauge.
  • the thickness of the negative electrode active material layer was determined by subtracting the thickness of the negative electrode current collector from the thickness of the test electrode 201 .
  • the thickness of the negative electrode active material layer was determined three times at three different arbitrary locations, and the average value of the three measurements was calculated.
  • a secondary battery was produced using the test electrode 201 according to the procedure described above, and then the secondary battery was charged.
  • the secondary battery was charged with a current of 0.2C until reaching a fully charged state.
  • 0.2C is a current value that can discharge the battery capacity in 5 hours.
  • a solvent dimethyl carbonate, which is an organic solvent
  • expansion rate (%) [(thickness after charging - thickness before charging)/thickness before charging] x 100 is used as an index for evaluating swelling characteristics. rate was calculated.
  • the type of the battery structure is not particularly limited.
  • the battery structure may be cylindrical, square, button, or the like.
  • the type of the element structure is not particularly limited.
  • the element structure may be a stacked type in which electrodes (positive and negative electrodes) are stacked, a zigzag-fold type in which electrodes are folded in a zigzag pattern, or other configurations.
  • the electrode reactant is lithium has been described, but the type of the electrode reactant is not particularly limited.
  • the electrode reactants may be other alkali metals such as sodium and potassium, or alkaline earth metals such as beryllium, magnesium and calcium, as described above.
  • the electrode reactant may be other light metals such as aluminum.

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Abstract

L'invention concerne un matériau actif comprenant, en tant qu'éléments constitutifs, un premier élément comprenant au moins un élément parmi le silicium, l'oxygène, le bore, et du phosphore, un second élément comprenant au moins un élément parmi un élément de métal alcalin, un élément de transition et un élément typique (à l'exclusion du silicium, de l'oxygène, du bore, du phosphore, des éléments de métal alcalin et des éléments de métal alcalino-terreux), et un troisième élément comprenant un élément de métal alcalino-terreux. La teneur en silicium dans les éléments constitutifs totaux à l'exclusion de l'oxygène et du carbone est de 60 à 98 % atomique (inclus), la teneur en premier élément dans les éléments constitutifs totaux est de 1 à 25 % atomique (inclus), la teneur en deuxième élément dans les éléments constitutifs totaux est de 1 à 34 % atomique (inclus), et la teneur en troisième élément dans les éléments constitutifs totaux est de 0 à 6 atomique % (inclus). Dans un spectre XPS (où l'axe horizontal est l'énergie de liaison (eV) et l'axe vertical est l'intensité spectrale) de Si2p mesuré à l'aide d'une spectroscopie photoélectronique à rayons X (XPS), un premier pic est détecté, le premier pic ayant une partie supérieure dans une plage dans laquelle l'énergie de liaison est de 102 à 105 eV (inclus), et un épaulement sur un côté de la partie supérieure où l'énergie de liaison est inférieure. Dans un spectre Raman (où l'axe horizontal est le décalage Raman (cm-1) et l'axe vertical est l'intensité spectrale) mesuré par spectroscopie Raman, deux pics ayant des sommets dans une plage dans laquelle le décalage Raman est de 435 cm-1 à 465 cm-1 (inclus) sont détectés. Le matériau actif a une pluralité de pores, et dans la distribution de pores (où l'axe horizontal est le diamètre de pore (µm) des pores et l'axe vertical est le taux de variation de pénétration du mercure) mesurée à l'aide de porosimétrie au mercure, un troisième pic est détecté, le troisième pic ayant une partie supérieure dans une plage dans laquelle le diamètre de pore est de 0,01 à 10 µm (inclus).
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